Exogenous sodium acetate (NaAc) can promote indole-3-acetic acid (IAA) synthesis during the primordium stage of Volvariella volvacea, thereby promoting primordium differentiation and increasing yield, but its specific mechanism of action has not been elucidated. This study aimed to analyze the ability of NaAc to induce IAA synthesis. Using a submerged culture method, a three-factor experiment was designed with five pH value gradients(6, 7, 8, 9, 10), four anions (Ac-, HCO3-, C5H7O5COO-, H2PO4-), and four cations (Na+, Mg2+, Mn2+, K+) to investigate the effects of adding NaAc on mycelial biomass and IAA synthesis, providing a theoretical basis for subsequently revealing the mechanism by which NaAc regulates IAA synthesis. The results showed that under pH value 8 conditions, mycelial biomass, aldehyde dehydrogenase (ALDH) activity, and the contents of IAA, indole-3-acetaldehyde (IAAld), indole-3-pyruvic acid (IPyA), tryptamine (TAM) and indole-3-acetaldoxime (IAOx) were significantly (p<0.05) increased by 37.98%, 58.39%, 61.29%, 58.33%, 31.25%, 29.23% and 64.71%, respectively. Among the anions, acetate ions (Ac-) significantly increased biomass, IAA content, and ALDH activity by 6.28%, 22.58%, and 21.01%, respectively, the contents of IPyA, TAM, and IAOx were also significantly higher than the control. Among the cations, Na+ significantly increased biomass, IAA content, and ALDH activity by 6.28%, 22.58% and 20.97%, respectively, and the contents of IPyA, TAM, and IAOx were also significantly higher than the control. This indicated that Na+ was superior to Mg2+, Mn2+, and K+ in promoting IAA synthesis. Comprehensive analysis showed that during the vegetative growth stage of V. volvacea, adding NaAc could maintain the culture environment pH value within an alkaline range suitable for growth. pH value, as the main regulatory factor after NaAc dissociation, together with Ac- and Na+, influenced biomass accumulation and IAA synthesis during the growth stage of V. volvacea.